We report on an experimental investigation of the low-energy stereodynamics of the energy transfer reactions Ne(3P2) + X, producing Ne(1S) + X+ and [Ne–X]+ (X = N2 or CO). Collision energies in the range 0.2 K–700 K are obtained by using the merged beam technique. Two kinds of product ions are generated by Penning and associative ionization, respectively. The intermediate product [Ne–X]+ in vibrationally excited states can predissociate into bare ions (X+). The experimental ratio of the NeX+ and X+ product ion yields is similar for both molecules at high collision energies but diverge at collision energies below 100 K. This difference is explained by the first excited electronic state of the product ions, which is accessible in the case of CO but lies too high in energy in the case of N2.